Bisphenol Hypersorbents for Enhanced Detection of, or Protection From, Hazardous Chemicals

ABSTRACT

The invention relates to strong hydrogen-bond acidic sorbents. The sorbents may be provided in a form that limits or eliminates intramolecular bonding of the hydrogen-bond acidic site between neighboring sorbent molecules, for example, by providing steric groups adjacent to the hydrogen-bond acidic site. The hydrogen bond site may be a phenolic structure based on a bisphenol architecture. The sorbents of the invention may be used in methods for trapping or detecting hazardous chemicals or explosives.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit as a division of U.S. patentapplication Ser. No. 16/178,488 filed on Nov. 1, 2018 which in turnclaims priority to U.S. Provisional Application No. 62/582,038, filed onNov. 6, 2017, the contents of each of which is incorporated herein byreference in its entirety.

FIELD OF THE INVENTION

This application relates generally to strong hydrogen-bond acidicsorbents. The sorbents may be provided in a form that limits oreliminates intermolecular bonding of one or more hydrogen-bond acidicsite(s) between neighboring sorbent molecules, for example, by providingsteric groups adjacent to the hydrogen-bond acidic site. Thehydrogen-bond site may be a phenolic structure based on a bisphenolarchitecture. The sorbents of the invention may be used in methods forthe detection, chromatographic separation, and trapping of hazardouschemicals, explosives, or related chemicals.

BACKGROUND OF THE INVENTION

Hypersorbents for targeting hydrogen-bond basic chemicals primarilyconsist of polymers with carbosilane, siloxane, or ether linkedbackbones that have been functionalized with strong hydrogen-bond acidicgroups to reversibly bind complimentary hydrogen-bond basic chemicals.Previously developed exemplary sorbents include fluoropolyol (FPOL),poly(oxy{methyl[4-hydroxy-4,4,bis(trifluoromethyl)but-1-en-1yl]silylene})(SXFA),poly(oxy{bis[4-hydroxy-4,4,bis(trifluoromethyl)but-1-en-1-yl]silylene})(SXFA2), andpoly(methyldi(1,1,1-trifluoro-2-trifluoromethyl-2-hydroxypent4-enyl)silane(HCFSA2, a hyperbranched carbosilane fluoroalcohol-based sorbentpolymer). Hexafluoroisopropanol groups are common motifs, included forexample, in SXFA, SXFA2 and HCSFA2 sorbents. The trifluoromethyl groupsaugment the hydrogen-bond acidity of the sorbents, which increases theinteractions with hydrogen-bond basic analytes of interest. In addition,they reduce the hydrogen-bond basicity of the oxygen atom in thehydroxyl by withdrawing electron density away from the oxygen.

However, a significant drawback to these and related sorbents withhydroxyl moieties is the propensity for self-association. Thisself-association, and to an extent the degree of self-association, canbe qualitatively or quantitatively assessed by infrared spectroscopy.For example, FIGS. 1A and 1B show the propensity of HCSFA2 toself-associate. There is only a small amount of free hydroxyl (—OH)visible, with most of the molecules' hydroxyl groups bonded to othergroups within the same sorbent molecule, or to other sorbent molecules.The existence of sorbent-sorbent hydrogen bonding, in any one instant,leads to a decrease in available sorbent-analyte binding sites, sorptionkinetics, and overall sorbent efficacy.

Accordingly, there is a need in the art for sorbents having bindingsites that are available to form sorbent-analyte bonds, and stericgroups that are able to prevent self-association among sorbents whilestill permitting sorbent-analyte binding.

SUMMARY OF THE INVENTION

The invention described herein, including the various aspects and/orembodiments thereof, meets the unmet needs of the art, as well asothers, by providing strong hydrogen-bond acidic sorbents. The sorbentsmay be provided in a form that limits or eliminates intra- orinter-molecular bonding of one or more hydrogen-bond acidic site(s)within a sorbent molecule, or between neighboring sorbent molecules, forexample, by providing steric groups adjacent to the hydrogen-bond acidicsite. The hydrogen-bond site may be a phenolic structure based on abisphenol architecture. The sorbents of the invention may be used inmethods for detecting, chromatographic separations, and trappinghazardous chemicals, explosives, or related chemicals.

In one aspect of the invention, a bisphenol sorbent is provided thatincludes a compound of Formula

where R¹ is selected from the group consisting of prop-1-en-2-yl;2-carboxyethyl; 1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl;(dipropylphosphoryl)oxy; dimethyl(phenyl)silyl; trimethyl silyl;hydroxy(phenyl)methyl; 4-ethylphenyl; 4-isopropylphenyl; 4-methylphenyl;4-(tert-butyl)phenyl; benzylideneamino; trimethylgermyl; acetylamino;diphenylmethyl; methylthio; acetyl(methyl)amino; benzoyl amino;2-propenyl; prop-2-enyl; triethylgermyl; benzyl; isobutyramido;(ethylcarbamothioyl)amino; bis(dimethylamino)phosphaneyl; hydroxy;4-methoxyphenyl; (diethoxyphosphoryl)methyl; ethylthio; diphenylamino;(methoxycarbonyl)amino; cyclopropyl; 4-(dimethylamino)butyl;2-(trimethylsilyl)ethyl; (diphenylphosphoryl)methyl;(dimethylamino)methyl; 2,2-dimethylpropyl; (ethoxycarbonyl)amino;2-methylpropyl; phenylethyl; propyl; butyl; sec-butyl;(butoxycarbonyl)amino; pentyl; heptyl; propan-2-yl;(4-methoxybenzoyl)amino; aminomethyl; carbamoylamino; cyclopentyl;2-hydroxy-2-methylpropyl; (4-methoxybenzylidene)amino; cyclohexyl;hydroxymethyl; cyclobutyl; 3-ethylpentan-3-yl; ethyl;1,1-dimethylpropyl; (trimethylsilyl)oxy; prop-2-enoxy; phenylamino;((trimethylsilyl)oxy)methyl; (trimethylsilyl)methyl; methoxy;hydroxyamino; 3,3-dimethyltriaz-1-en-1-yl; ethoxy; ethylcarbamoylamino;butoxy; propoxy; (dipropylphosphoryl)amino; pentyloxy; propan-2-yloxy;(1-(phenylamino)ethylidene)amino; amino; methylamino; hydrazinyl;ethylamino; butylamino; diethylamino; dimethylamino; dipropylamino;((difluoromethaneidyl)oxy)difluoromethyl; 3-oxidopropoxy; 2-oxidoethoxy;sulfonato; hydroxyoxidophosphoryl; sulfinato; 2-(carboxylatomethy)l;carboxylate; (hydroxyoxidophosphoryl)oxy; propan-1-id-3-yl; nitroamido;trihydroxyborato; sulfido; oxidomethoxy; oxido; trifluoromethyl; andfluoro; andR² is selected from the group consisting of hydrogen, prop-1-en-2-yl;2-carboxyethyl; 1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl;(dipropylphosphoryl)oxy; dimethyl(phenyl)silyl; trimethylsilyl;hydroxy(phenyl)methyl; 4-ethylphenyl; 4-isopropylphenyl; 4-methylphenyl;4-(tert-butyl)phenyl; benzylideneamino; trimethylgermyl; acetylamino;diphenylmethyl; methylthio; acetyl(methyl)amino; benzoylamino;2-propenyl; prop-2-enyl; triethylgermyl; benzyl; isobutyramido;(ethylcarbamothioyl)amino; bis(dimethylamino)phosphaneyl; hydroxy;4-methoxyphenyl; (diethoxyphosphoryl)methyl; ethylthio; diphenylamino;(methoxycarbonyl)amino; cyclopropyl; 4-(dimethylamino)butyl;2-(trimethylsilyl)ethyl; (diphenylphosphoryl)methyl;(dimethylamino)methyl; 2,2-dimethylpropyl; (ethoxycarbonyl)amino;2-methylpropyl; phenylethyl; propyl; butyl; sec-butyl;(butoxycarbonyl)amino; pentyl; heptyl; propan-2-yl;(4-methoxybenzoyl)amino; aminomethyl; carbamoylamino; cyclopentyl;2-hydroxy-2-methylpropyl; (4-methoxybenzylidene)amino; cyclohexyl;hydroxymethyl; cyclobutyl; 3-ethylpentan-3-yl; ethyl;1,1-dimethylpropyl; (trimethylsilyl)oxy; prop-2-enoxy; phenylamino;((trimethylsilyl)oxy)methyl; (trimethylsilyl)methyl; methoxy;hydroxyamino; 3,3-dimethyltriaz-1-en-1-yl; ethoxy; ethylcarbamoylamino;butoxy; propoxy; (dipropylphosphoryl)amino; pentyloxy; propan-2-yloxy;(1-(phenylamino)ethylidene)amino; amino; methylamino; hydrazinyl;ethylamino; butylamino; diethylamino; dimethylamino; dipropylamino;((difluoromethaneidyl)oxy)difluoromethyl; 3-oxidopropoxy; 2-oxidoethoxy;sulfonato; hydroxyoxidophosphoryl; sulfinato; 2-(carboxylatomethy)l;carboxylate; (hydroxyoxidophosphoryl)oxy; propan-1-id-3-yl; nitroamido;trihydroxyborato; sulfido; oxidomethoxy; oxido; trifluoromethyl; andfluoro.

In another aspect of the invention, a bisphenol sorbent is provided thatincludes a compound of Formula II

where R¹ is selected from the group consisting of prop-1-en-2-yl;2-carboxyethyl; 1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl;(dipropylphosphoryl)oxy; dimethyl(phenyl)silyl; trimethylsilyl;hydroxy(phenyl)methyl; 4-ethylphenyl; 4-isopropylphenyl; 4-methylphenyl;4-(tert-butyl)phenyl; benzylideneamino; trimethylgermyl; acetylamino;diphenylmethyl; methylthio; acetyl(methyl)amino; benzoylamino;2-propenyl; prop-2-enyl; triethylgermyl; benzyl; isobutyramido;(ethylcarbamothioyl)amino; bis(dimethylamino)phosphaneyl; hydroxy;4-methoxyphenyl; (diethoxyphosphoryl)methyl; ethylthio; diphenylamino;(methoxycarbonyl)amino; cyclopropyl; 4-(dimethylamino)butyl;2-(trimethylsilyl)ethyl; (diphenylphosphoryl)methyl;(dimethylamino)methyl; 2,2-dimethylpropyl; (ethoxycarbonyl)amino;2-methylpropyl; phenylethyl; propyl; butyl; sec-butyl;(butoxycarbonyl)amino; pentyl; heptyl; methyl; propan-2-yl;(4-methoxybenzoyl)amino; aminomethyl; carbamoylamino; cyclopentyl;2-hydroxy-2-methylpropyl; (4-methoxybenzylidene)amino; cyclohexyl;hydroxymethyl; tert-butyl; cyclobutyl; 3-ethylpentan-3-yl; ethyl;1,1-dimethylpropyl; (trimethylsilyl)oxy; prop-2-enoxy; phenylamino;((trimethylsilyl)oxy)methyl; (trimethylsilyl)methyl; methoxy; hydroxyamino; 3,3-dimethyltriaz-1-en-1-yl; ethoxy; ethylcarbamoylamino; butoxy;propoxy; (dipropylphosphoryl)amino; pentyloxy; propan-2-yloxy;(1-(phenylamino)ethylidene)amino; amino; methylamino; hydrazinyl;ethylamino; butylamino; diethylamino; dimethylamino; dipropylamino;((difluoromethaneidyl)oxy)difluoromethyl; 3-oxidopropoxy; 2-oxidoethoxy;sulfonato; hydroxyoxidophosphoryl; sulfinato; 2-(carboxylatomethy)l;carboxylate; (hydroxyoxidophosphoryl)oxy; propan-1-id-3-yl; nitroamido;trihydroxyborato; sulfido; oxidomethoxy; oxido; trifluoromethyl; andfluoro; andR² is selected from the group consisting of hydrogen, prop-1-en-2-yl;2-carboxyethyl; 1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl;(dipropylphosphoryl)oxy; dimethyl(phenyl)silyl; trimethylsilyl;hydroxy(phenyl)methyl; 4-ethylphenyl; 4-isopropylphenyl; 4-methylphenyl;4-(tert-butyl)phenyl; benzylideneamino; trimethylgermyl; acetylamino;diphenylmethyl; methylthio; acetyl(methyl)amino; benzoylamino;2-propenyl; prop-2-enyl; triethylgermyl; benzyl; isobutyramido;(ethylcarbamothioyl)amino; bis(dimethylamino)phosphaneyl; hydroxy;4-methoxyphenyl; (diethoxyphosphoryl)methyl; ethylthio; diphenylamino;(methoxycarbonyl)amino; cyclopropyl; 4-(dimethylamino)butyl;2-(trimethylsilyl)ethyl; (diphenylphosphoryl)methyl;(dimethylamino)methyl; 2,2-dimethylpropyl; (ethoxycarbonyl)amino;2-methylpropyl; phenylethyl; propyl; butyl; sec-butyl;(butoxycarbonyl)amino; pentyl; heptyl; methyl; propan-2-yl;(4-methoxybenzoyl)amino; aminomethyl; carbamoylamino; cyclopentyl;2-hydroxy-2-methylpropyl; (4-methoxybenzylidene)amino; cyclohexyl;hydroxymethyl; tert-butyl; cyclobutyl; 3-ethylpentan-3-yl; ethyl;1,1-dimethylpropyl; (trimethylsilyl)oxy; prop-2-enoxy; phenylamino;((trimethylsilyl)oxy)methyl; (trimethylsilyl)methyl; methoxy;hydroxyamino; 3,3-dimethyltriaz-1-en-1-yl; ethoxy; ethylcarbamoylamino;butoxy; propoxy; (dipropylphosphoryl)amino; pentyloxy; propan-2-yloxy;(1-(phenylamino)ethylidene)amino; amino; methylamino; hydrazinyl;ethylamino; butylamino; diethylamino; dimethylamino; dipropylamino;((difluoromethaneidyl)oxy)difluoromethyl; 3-oxidopropoxy; 2-oxidoethoxy;sulfonato; hydroxyoxidophosphoryl; sulfinato; 2-(carboxylatomethy)l;carboxylate; (hydroxyoxidophosphoryl)oxy; propan-1-id-3-yl; nitroamido;trihydroxyborato; sulfido; oxidomethoxy; oxido; trifluoromethyl; andfluoro.

In a further aspect of the invention, a method for detecting an analytehaving one or more hydrogen-bond basic groups is provided, including:providing a bisphenol sorbent of Formula I or Formula II having stericgroups R¹ and R²,

wherein R¹ is selected from the group consisting of prop-1-en-2-yl;2-carboxyethyl; 1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl;(dipropylphosphoryl)oxy; dimethyl(phenyl)silyl; trimethylsilyl;hydroxy(phenyl)methyl; 4-ethylphenyl; 4-isopropylphenyl; 4-methylphenyl;4-(tert-butyl)phenyl; benzylideneamino; trimethylgermyl; acetylamino;diphenylmethyl; methylthio; acetyl(methyl)amino; benzoylamino;2-propenyl; prop-2-enyl; triethylgermyl; benzyl; isobutyramido;(ethylcarbamothioyl)amino; bis(dimethylamino)phosphaneyl; hydroxy;4-methoxyphenyl; (diethoxyphosphoryl)methyl; ethylthio; diphenylamino;(methoxycarbonyl)amino; cyclopropyl; 4-(dimethylamino)butyl;2-(trimethylsilyl)ethyl; (diphenylphosphoryl)methyl;(dimethylamino)methyl; 2,2-dimethylpropyl; (ethoxycarbonyl)amino;2-methylpropyl; phenylethyl; propyl; butyl; sec-butyl;(butoxycarbonyl)amino; pentyl; heptyl; methyl; propan-2-yl;(4-methoxybenzoyl)amino; aminomethyl; carbamoylamino; cyclopentyl;2-hydroxy-2-methylpropyl; (4-methoxybenzylidene)amino; cyclohexyl;hydroxymethyl; tert-butyl; cyclobutyl; 3-ethylpentan-3-yl; ethyl;1,1-dimethylpropyl; (trimethylsilyl)oxy; prop-2-enoxy; phenylamino;((trimethylsilyl)oxy)methyl; (trimethylsilyl)methyl; methoxy; hydroxyamino; 3,3-dimethyltriaz-1-en-1-yl; ethoxy; ethylcarbamoylamino; butoxy;propoxy; (dipropylphosphoryl)amino; pentyloxy; propan-2-yloxy;(1-(phenylamino)ethylidene)amino; amino; methylamino; hydrazinyl;ethylamino; butylamino; diethylamino; dimethylamino; dipropylamino;((difluoromethaneidyl)oxy)difluoromethyl; 3-oxidopropoxy; 2-oxidoethoxy;sulfonato; hydroxyoxidophosphoryl; sulfinato; 2-(carboxylatomethy)l;carboxylate; (hydroxyoxidophosphoryl)oxy; propan-1-id-3-yl; nitroamido;trihydroxyborato; sulfido; oxidomethoxy; oxido; trifluoromethyl; andfluoro; and R² is selected from the group consisting of hydrogen,prop-1-en-2-yl; 2-carboxyethyl;1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl; (dipropylphosphoryl)oxy;dimethyl(phenyl)silyl; trimethylsilyl; hydroxy(phenyl)methyl;4-ethylphenyl; 4-isopropylphenyl; 4-methylphenyl; 4-(tert-butyl)phenyl;benzylideneamino; trimethylgermyl; acetylamino; diphenylmethyl;methylthio; acetyl(methyl)amino; benzoylamino; 2-propenyl; prop-2-enyl;triethylgermyl; benzyl; isobutyramido; (ethylcarbamothioyl)amino;bis(dimethylamino)phosphaneyl; hydroxy; 4-methoxyphenyl;(diethoxyphosphoryl)methyl; ethylthio; diphenylamino;(methoxycarbonyl)amino; cyclopropyl; 4-(dimethylamino)butyl;2-(trimethylsilyl)ethyl; (diphenylphosphoryl)methyl;(dimethylamino)methyl; 2,2-dimethylpropyl; (ethoxycarbonyl)amino;2-methylpropyl; phenylethyl; propyl; butyl; sec-butyl;(butoxycarbonyl)amino; pentyl; heptyl; methyl; propan-2-yl;(4-methoxybenzoyl)amino; aminomethyl; carbamoylamino; cyclopentyl;2-hydroxy-2-methylpropyl; (4-methoxybenzylidene)amino; cyclohexyl;hydroxymethyl; tert-butyl; cyclobutyl; 3-ethylpentan-3-yl; ethyl;1,1-dimethylpropyl; (trimethylsilyl)oxy; prop-2-enoxy; phenylamino;((trimethylsilyl)oxy)methyl; (trimethylsilyl)methyl; methoxy; hydroxyamino; 3,3-dimethyltriaz-1-en-1-yl; ethoxy; ethylcarbamoylamino; butoxy;propoxy; (dipropylphosphoryl)amino; pentyloxy; propan-2-yloxy;(1-(phenylamino)ethylidene)amino; amino; methylamino; hydrazinyl;ethylamino; butylamino; diethylamino; dimethylamino; dipropylamino;((difluoromethaneidyl)oxy)difluoromethyl; 3-oxidopropoxy; 2-oxidoethoxy;sulfonato; hydroxyoxidophosphoryl; sulfinato; 2-(carboxylatomethy)l;carboxylate; (hydroxyoxidophosphoryl)oxy; propan-1-id-3-yl; nitroamido;trihydroxyborato; sulfido; oxidomethoxy; oxido; trifluoromethyl; andfluoro; and contacting the bisphenol sorbent with an analyte having oneor more hydrogen-bond basic groups, where the bisphenol selectivelybinds with analytes having one or more hydrogen-bond basic groups thatcircumvent steric groups R¹ and R², forming a bisphenol sorbent-analytephysisorption bond.

In some aspects of the invention, binding with an analyte produceschanges in infrared spectral properties that are used as the basis foridentifying the bound analyte. The bisphenol sorbent preferentially andselectively binds with stronger hydrogen-bond basic analytes of interestover more weakly-basic interferents.

In other aspects of the invention, a method for collecting an analytehaving one or more hydrogen-bond basic groups is provided, whichincludes providing a bisphenol sorbent having a compound of Formula I orFormula II, wherein R¹ and R² are as described above, and contacting thebisphenol sorbent with a sample including the analyte, wherein thebisphenol selectively binds with the stronger hydrogen-bond basicanalyte as compared to weaker hydrogen-bond basic interferents, formingbisphenol sorbent-analyte physisorption bonds.

In still further aspects of the invention, a method for separating ahydrogen-bond basic analyte from a mixture is provided, which includesas a chromatographic stationary phase a bisphenol sorbent comprising acompound of Formula I or Formula II, wherein R¹ and R² are as describedabove, and contacting the bisphenol sorbent with a sample comprising ahydrogen-bond basic analyte, wherein the bisphenol sorbent selectivelybinds with hydrogen-bond basic analyte molecules having higherhydrogen-bond basicity over other chemicals having lower hydrogen-bondbasicity.

In additional aspects of the invention, a method for forming a polymericarticle having a reduced risk of causing endocrine disruption isprovided, which includes forming a polymeric article by polymerizationof a reaction mixture comprising a bisphenol monomer of Formula A orFormula B, wherein R¹ and R² are as described above. The formedpolymeric article comprises free bisphenol monomer of Formula A orFormula B, and wherein upon leaching out of the polymeric article thefree bisphenol monomer of Formula A or Formula B causes a reduced levelof endocrine disruption as compared to conventional bisphenol monomersthat leach out of polymeric articles formed by polymerizing a reactionmixture comprising conventional bisphenol monomers.

Other features and advantages of the present invention will becomeapparent to those skilled in the art upon examination of the followingor upon learning by practice of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A-1F illustrate the problems with existing sorbent molecules, andthe solution of the present invention.

In FIG. 1A, the IR spectrum and structure of HCSFA2 are shown.

FIG. 1B illustrates intermolecular bonding of HCSFA2 sorbents betweenhexafluoroisopropanol functional groups or between ahexafluoroisopropanol group and another sorbent feature.

FIG. 1C illustrates the IR spectrum and hyperbranched structure ofHCSFA2.

FIG. 1D illustrates an example of a steric protection of phenolichydroxyl groups with isopropyl groups, to prevent or reduceintermolecular bonding of sorbent molecules with a bisphenolarchitecture.

FIG. 1E outlines the problem to be solved, and the approach taken by thesorbent molecules of the invention.

FIG. 1F illustrates several bisphenol sorbent molecules in accordancewith the invention.

FIG. 1G provides vapor-sorbent ATR-IR differential spectra for thesorbent HCSFA2 at different concentrations of DMMP, illustrating thespectral changes in the MWIR and LWIR, providing the basis of an IRsensing path to detecting a chemical of interest.

FIG. 2 shows the infrared spectrum and structure of newly developedsorbent4,4′-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2,6-di-tert-butylphenol].

FIG. 3 shows the infrared spectrum and structure of newly developedsorbent4,4′-(perfluoropropane-2,2-diyl)bis(2-allyl-6-(tert-pentyl)phenol).

FIG. 4 shows the infrared spectrum and structure of known sorbent4,4′-(perfluoropropane-2,2-diyl)bis(2,6-dimethylphenol).

FIG. 5 shows an overlay of the IR spectra of bisphenols 3, 10, and 30.

FIGS. 6A-6D show synthetic schemes for bisphenols of the invention, anda summary of the bisphenol sorbents.

FIG. 7 shows IR spectra for vapor-sorbent binding data for the bisphenol10 sorbent exposed to an example vapor.

FIG. 8 shows the differential IR spectrum of bisphenol sorbent 10interacting with DMMP vapor.

FIG. 9 shows the response of a QCM sensor coated with bisphenol 10 toDMMP vapor at a concentration of 1 ppm.

FIG. 10 is a normalized graph of the response of a QCM sensor coatedwith bisphenol 10 to DMMP vapor at a concentration of 1 ppm.

DETAILED DESCRIPTION OF THE INVENTION

The invention described herein, including the various aspects and/orembodiments thereof, meets the unmet needs of the art, as well asothers, by providing strong hydrogen-bond acidic sorbents. The sorbentsmay be provided in a form that limits or eliminates intra- orinter-molecular bonding of the hydrogen-bond acidic site within asorbent molecule or between neighboring sorbent molecules, respectively,for example, by providing alkyl steric groups adjacent to thehydrogen-bond acidic site. The hydrogen bond site may be a phenolicstructure based on a bisphenol architecture.

The sorbents of the invention may be used in methods for binding tochemicals having hydrogen-bond basic properties, which are present inmany toxic or hazardous chemicals. Chemicals that may be bound using thesorbents and methods of the invention include chemical warfare agents(CWAs), toxic industrial chemicals (TICs), and explosives that exhibithydrogen-bond basic properties, as may be determined by those skilled inthe art. These chemicals include, but are not limited to, amines (i.e.,TEA (triethylamine)), TPA (tripropylamine), BuAm (butylamine), ammonia),arsines, acetone, acetonitrile, pyridine, DMSO (dimethylsulfoxide),organophosphonates (i.e., DMMP (dimethyl methylphosphonate)),organophosphates (i.e., DIFP (diisopropyl fluorophosphates)), TATP(triacetone triperoxide), and derivatives of phosphonic acid (i.e., theV-series nerve agents, VE(O-ethyl-S[2-(diethylamino)ethyl]ethylphosphonothioate), VG(0,0-diethyl-S[2-(diethylamino)ethyl]phosphorothioate), VM(O-ethyl-S-[2-(diethylamino)ethyl]methylphosphonothioate), and VX(O-ethyl S-(2-diisopropylaminoethyl)methylphosphonothioate)). Explosivesthat have hydrogen-bond basic properties may also be detected using thesensors, systems, and methods of the invention, including, but notlimited to, TNT (2-methyl-1,3,5-trinitrobenzene), TEX(4,10-dinitro-2,6,8,12-tetraoxa-4,10-diazatetracyclo[5.5.0.0^(5,9).0^(3,11)]-dodecane),HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), CL-20(2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazatetracyclo[5.5.0.0^(3,11).0^(5,9)]dodecane),and RDX (1,3,5-trinitro-1,3,5-triazinane), as well as additionalexplosives as may be determined by those skilled in the art.

The sorbents of the invention may be based on a bisphenol compound, forexample, bisphenol A hexafluoride (bisphenol AF, CAS 1478-61-1). Thebisphenol compound is ortho- or meta-substituted with one or more stericgroups to protect the hydroxyl moieties. Preferably, the steric groupsare alkyl groups, and each of the steric groups may be the same ordifferent. These bisphenol sorbents provide strong acidic hydrogen-bond(HB) sites that are protected from self-association or association withother relatively large molecules.

Additional bisphenols suitable for substitution with the steric groupsof the invention include, but are not limited to, bisphenol S (CAS80-09-1), bisphenol C2 (CAS 14868-03-2), bisphenol A (CAS 80-05-7),bisphenol AP (CAS 1571-75-1), bisphenol B (CAS 77-40-7), bisphenol BP(CAS 1844-01-5), bisphenol C (CAS 79-97-0), bisphenol E (CAS 2081-08-5),bisphenol F (CAS 620-92-8), bisphenol G (CAS 127-54-8), bisphenol M (CAS13595-25-0), bisphenol P (CAS 2167-51-3), bisphenol TMC (CAS129188-99-4), and bisphenol Z (CAS 843-55-0).

The bisphenol sorbents of the invention preferably comprise a compoundof formula A.

X and X′ may be selected from hydrogen, methyl, benzyl, trifluoromethyl,ethyl, phenyl, or taken together may form dichloroethene, sulfone,propylbenzene, or an optionally alkyl-substituted cyclic alkyl groupsuch as cyclohexane or 3,3,5-trimethyl cyclohexane. The compounds offormula A include the R¹ and R² substituents in an ortho orientationwith respect to the hydroxyl group. In some aspects of the invention, itmay be preferable to provide the substituents in the meta position withrespect to the hydroxyl group, as shown in formula B.

R¹ may be any substituent shown in Table 1 (below), and R² is eitherhydrogen (H) or any substituent shown in Table 1 (Remya, G. S. et al.,Phys. Chem. Chem. Phys. 2016, 18, 20615-20626). By selectingsubstituents from Table 1, which are relatively bulky but with lessinductively electron donating effects than alkyl substituents, it ispossible to retain more of the strong hydrogen-bond acidity at thephenolic hydroxyl.

TABLE 1 Substituent ΔV_(c) C(Me)═CH₂ −0.

S^(>) CH₂CH₂COOH −0.3 S^(>) Si(Me)(OSiMe

)₂ −0.7 S^(>) OPO(C₆H

)

−0.7 S^(>) Si(C₆H

)Me

−0.7 S^(>) SIMe₃ −0.9 S^(>) CH(OH)C

H

−1.0 S^(>) C₆H₄—4Et −1.1 S^(>) C₆H₄—4CHMe₂ −1.2 S^(>) C₆H₄—4Me −1.2S^(>) C₆H₄—4CMe₃ −1.2 S^(>) N═CHC₆H

−1.3 S^(>) GeMe

−1.4 S^(>) NHCOMe −1.4 S^(>) CH(C₆H₅)₂ −1.4 S^(>) SMe −1.5 S^(>) NMeCOMe−1.5 S^(>) NHCOC₆H₅ −1.5 S^(>) CH₂CH═CH₂ −1.6 S^(>) Ge(Et)

−1.6 S^(>) CH₂C₆H₅ −1.8 S^(>) NHCOCH(Me)₂ −1.8 S^(>) NHCSNHEt −1.8 S^(>)P(N(Me)₂)₂ −1.9 S^(>) OH −2.0 S^(>) C₆H₄—4OMe −2.0 S^(>) CH₂PD(OEt)₂−2.0 S^(>) SEt −2.2 S^(>) N(C₆H

)₂ −2.3 S^(>) NHCOOMe −2.4 S^(>) Cyclopropryl −2.4 S^(>) (CH

)

NMe₂ −2.4 S^(>) CH₂CH₂Si(Me)

−2.4 S^(>) CH₂PO(C₆H₅)₂ −2.5 S^(>) CH₂NMe₂ −2.6 S^(>>) CH₂C(Me)

−2.9 S^(>>) NHCOOEt −3.0 S^(>>) CH₂CH(Me)₂ −3.0 S^(>>) CH₂CH₂C₆H₅ −3.1S^(>>) CH₂CH₂CH₃ −3.1 S^(>>) (CH₂)

CH

−3.2 S^(>>) CH(Me)(Et) −3.2 S^(>>) NHCOO(CH₂)₃CH₃ −3.2 S^(>>) (CH₂)₄CH

−3.2 S^(>>) (CH₂)₆CH₃ −3.2 S^(>>) Me −3.3 S^(>>) Isopropyl −3.3 S^(>>)NHCOC₆H

—4OMe −3.4 S^(>>) CH₂NH₂ −3.5 S^(>>) NHCONH₂ −3.7 S^(>>) Cyclopentyl−3.7 S^(>>) CH₂C(OH)(Me)₂ −3.7 S^(>>) N═CHC₆H₄-4-OMe −3.8 S^(>>)Cyclohexyl −3.8 S^(>>) CH₂OH −3.8 S^(>>) C(Me)₃ −3.9 S^(>>) Cyclobutyl−3.9 S^(>>) C(Et)₃ −4.0 S^(>>) Et −4.0 S^(>>) C(Et)(Me)₂ −4.2 S^(>>)OSiMe₃ −4.2 S^(>>) OCH₂CH═CH₂ −4.8 S^(>>) NHC₆H₅ −4.8 S^(>>) CH₂OSi(CH₃)

−4.8 S^(>>) CH₂Si(Me)

−4.9 S^(>>) OMe −5.0 S^(>>) NHOH −5.1 S^(>>) N═NNMe₂ −5.6 S^(>>) OCH₂CH₃−5.8 S^(>>) NHCONHEt −5.8 S^(>>) O(CH₂)

CH₃ −5.9 S^(>>) OCH₂CH₂CH₃ −6.0 S^(>>) NHPO(C₃H

)₂ −6.2 S^(>>) O(CH₂)₄CH₃ −6.2 S^(>>) OCHMe₂ −6.5 S^(>>) N═C(Me)NHC₆H₅−6.6 S^(>>) NH₂ −9.0 S^(>>>) NHMe −11.2 S^(>>>) NHNH₂ −11.2 S^(>>>) NHEt−11.4 S^(>>>) NH(CH

)

CH

−11.6 S^(>>>) N(Et)₂ −11.9 S^(>>>) N(Me)₂ −12.3 S^(>>>) N(C₃H₇)₂ −12.9S^(>>>) CF₂OCF₂ ⁻ −57.6 S^(>>>) OCH₂CH₂CH₂O⁻ −63.2 S^(>>>>) OCH₂CH₂O⁻−66.8 S^(>>>>) SO₃ ⁻ −67.2 S^(>>>>) PO₃H⁻ −70.4 S^(>>>>) SO₂ ⁻ −73.2S^(>>>>) CH₂CO₂ ⁻ −74.5 S^(>>>>) CO₂ ⁻ −77.6 S^(>>>>) OPO₃H⁻ −83.2S^(>>>>) CH₂CH₂CH₂ ⁻ −83.7 S^(>>>>) NNO₂ ⁻ −88.9 S^(>>>>) B(OH)₃ ⁻ −88.9S^(>>>>) S⁻ −99.8 S^(>>>>) OCH₂O⁻ −102.6 S^(>>>>) O⁻ −113.4 S^(>>>>)

indicates data missing or illegible when filed

The invention further relates to bisphenols of formula I and formula II,

where R¹ is a substituent selected from prop-1-en-2-yl; 2-carboxyethyl;1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl; (dipropylphosphoryl)oxy;dimethyl(phenyl)silyl; trimethyl silyl; hydroxy(phenyl)methyl;4-ethylphenyl; 4-isopropylphenyl; 4-methylphenyl; 4-(tert-butyl)phenyl;benzylideneamino; trimethylgermyl; acetylamino; diphenylmethyl;methylthio; acetyl(methyl)amino; benzoylamino; 2-propenyl; prop-2-enyl;triethylgermyl; benzyl; isobutyramido; (ethylcarbamothioyl)amino;bis(dimethylamino)phosphaneyl; hydroxy; 4-methoxyphenyl;(diethoxyphosphoryl)methyl; ethylthio; diphenylamino;(methoxycarbonyl)amino; cyclopropyl; 4-(dimethylamino)butyl;2-(trimethylsilyl)ethyl; (diphenylphosphoryl)methyl;(dimethylamino)methyl; 2,2-dimethylpropyl; (ethoxycarbonyl)amino;2-methylpropyl; phenylethyl; propyl; butyl; sec-butyl;(butoxycarbonyl)amino; pentyl; heptyl; methyl; propan-2-yl;(4-methoxybenzoyl)amino; aminomethyl; carbamoylamino; cyclopentyl;2-hydroxy-2-methylpropyl; (4-methoxybenzylidene)amino; cyclohexyl;hydroxymethyl; tert-butyl; cyclobutyl; 3-ethylpentan-3-yl; ethyl;1,1-dimethylpropyl; (trimethylsilyl)oxy; prop-2-enoxy; phenylamino;((trimethylsilyl)oxy)methyl; (trimethylsilyl)methyl; methoxy; hydroxyamino; 3,3-dimethyltriaz-1-en-1-yl; ethoxy; ethylcarbamoylamino; butoxy;propoxy; (dipropylphosphoryl)amino; pentyloxy; propan-2-yloxy;(1-(phenylamino)ethylidene)amino; amino; methylamino; hydrazinyl;ethylamino; butylamino; diethylamino; dimethylamino; dipropylamino;((difluoromethaneidyl)oxy)difluoromethyl; 3-oxidopropoxy; 2-oxidoethoxy;sulfonato; hydroxyoxidophosphoryl; sulfinato; 2-(carboxylatomethy)l;carboxylate; (hydroxyoxidophosphoryl)oxy; propan-1-id-3-yl; nitroamido;trihydroxyborato; sulfido; oxidomethoxy; oxido; trifluoromethyl; andfluoro.

R² is hydrogen or a substituent selected from prop-1-en-2-yl;2-carboxyethyl; 1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl;(dipropylphosphoryl)oxy; dimethyl(phenyl)silyl; trimethyl silyl;hydroxy(phenyl)methyl; 4-ethylphenyl; 4-isopropylphenyl; 4-methylphenyl;4-(tert-butyl)phenyl; benzylideneamino; trimethylgermyl; acetylamino;diphenylmethyl; methylthio; acetyl(methyl)amino; benzoylamino;2-propenyl; prop-2-enyl; triethylgermyl; benzyl; isobutyramido;(ethylcarbamothioyl)amino; bis(dimethylamino)phosphaneyl; hydroxy;4-methoxyphenyl; (diethoxyphosphoryl)methyl; ethylthio; diphenylamino;(methoxycarbonyl)amino; cyclopropyl; 4-(dimethylamino)butyl;2-(trimethylsilyl)ethyl; (diphenylphosphoryl)methyl;(dimethylamino)methyl; 2,2-dimethylpropyl; (ethoxycarbonyl)amino;2-methylpropyl; phenylethyl; propyl; butyl; sec-butyl;(butoxycarbonyl)amino; pentyl; heptyl; methyl; propan-2-yl;(4-methoxybenzoyl)amino; aminomethyl; carbamoylamino; cyclopentyl;2-hydroxy-2-methylpropyl; (4-methoxybenzylidene)amino; cyclohexyl;hydroxymethyl; tert-butyl; cyclobutyl; 3-ethylpentan-3-yl; ethyl;1,1-dimethylpropyl; (trimethylsilyl)oxy; prop-2-enoxy; phenylamino;((trimethylsilyl)oxy)methyl; (trimethylsilyl)methyl; methoxy; hydroxyamino; 3,3-dimethyltriaz-1-en-1-yl; ethoxy; ethylcarbamoylamino; butoxy;propoxy; (dipropylphosphoryl)amino; pentyloxy; propan-2-yloxy;(1-(phenylamino)ethylidene)amino; amino; methylamino; hydrazinyl;ethylamino; butylamino; diethylamino; dimethylamino; dipropylamino;((difluoromethaneidyl)oxy)difluoromethyl; 3-oxidopropoxy; 2-oxidoethoxy;sulfonato; hydroxyoxidophosphoryl; sulfinato; 2-(carboxylatomethy)l;carboxylate; (hydroxyoxidophosphoryl)oxy; propan-1-id-3-yl; nitroamido;trihydroxyborato; sulfido; oxidomethoxy; oxido; trifluoromethyl; andfluoro.

The invention additionally relates to di-substituted bisphenols, whereR¹ is a substituent selected from the substituents above (other thanhydrogen), and R² is hydrogen. Such di-substituted bisphenols are named4,4′-(perfluoropropane-2,2-diyl)bis(2-(substituent)phenol).

The invention also relates to tetra-substituted bisphenols where R¹ andR² are the same substituent, and are selected from the substituentsabove (other than hydrogen). Such tetra-substituted bisphenols are named4,4′-(perfluoropropane-2,2-diyl)bis(2,6-di(substituent)phenol).

The invention further relates to tetra-substituted bisphenols where R¹and R² are different substituents selected from the substituents above(neither is hydrogen). Such tetra-substituted bisphenols are named4,4′-(perfluoropropane-2,2-diyl)bis(3-(first substituent)-5-(secondsubstituent)phenol).

The invention additionally relates to di-substituted bisphenols, whereR¹ is a substituent selected from the substituents above (other thanhydrogen), and R² is hydrogen. Such di-substituted bisphenols are named4,4′-(perfluoropropane-2,2-diyl)bis(3-(substituent)phenol).

The invention also relates to tetra-substituted bisphenols where R¹ andR² are the same substituent, and are selected from the substituentsabove (other than hydrogen). Such tetra-substituted bisphenols are named4,4′-(perfluoropropane-2,2-diyl)bis(3,5-di(substituent)phenol).

The invention further relates to tetra-substituted bisphenols where R¹and R² are different substituents, and are selected from thesubstituents above (other than hydrogen). Such tetra-substitutedbisphenols are named 4,4′-(perfluoropropane-2,2-diyl)bis(3-(firstsubstituent)-5-(second substituent)phenol).

The invention additionally relates to combinations of two or more of thebisphenol sorbents of the invention together in an admixture to effect achange in the solid physical properties of one bisphenol with a liquidlike bisphenol.

In this invention, one or more acidic hydrogen-bond (HB) sites in thesorbent molecule are protected by an ortho- or meta-substituted phenolicstructure. Preferably at least half of the HB sites in the sorbentmolecule are present in the free hydroxyl form at any one time. Morepreferably, about 75% of the HB sites in the molecule are present in thefree hydroxyl form. According to some presently-preferred aspects,greater than 95% of the HB sites in the sorbent molecule are present inthe free hydroxyl form. To prevent intermolecular bonding between thehydrogen-bond acidic sites and neighboring sorbent molecules, alkylsteric groups may be provided in different positions neighboring the HBacid site to limit or eliminate the approach of relatively largemolecules, such as the sorbent itself. By synthesizing and testingvarious alkylated phenolic structures, the invention has identified howlarge the alkylated structures need to be to successfully prevent theundesirable intermolecular bonding between the hydrogen-bond acidicsites and neighboring sorbent molecules. When R¹ and/or R² is methyl(1C), ethyl (2C), and propyl (3C), the substituents may not provideenough steric hindrance to prevent intermolecular hydrogen bondingbetween bisphenol type sorbent molecules. As the steric groups increasein both size and amount of branching, the amount of free hydroxylincreases. In one aspect of the invention, a bisphenol sorbent whereR¹=propyl and R²=1,1-dimethylpropyl is preferred. This sorbent maximizesthe amount of free hydroxyl and also presents in an ideal physicalstate, a viscous oil, to allow rapid analyte uptake.

Additional preferred bisphenol sorbents in accordance with the inventioninclude 4,4′-(perfluoropropane-2,2-diyl)bis(2-propylphenol),4,4′-(perfluoropropane-2,2-diyl)bis(2,6-di-tert-butylphenol),4,4′-(perfluoropropane-2,2-diyl)bis(2-(tert-pentyl)phenol),4,4′-(perfluoropropane-2,2-diyl)bis(2-(tert-pentyl)-6-propylphenol),4,4′-(perfluoropropane-2,2-diyl)bis(2,6-dipropylphenol),4,4′-(perfluoropropane-2,2-diyl)bis(2,6-dimethylphenol),4,4′-(perfluoropropane-2,2-diyl)bis(2,6-diethylphenol),4,4′-(perfluoropropane-2,2-diyl)bis(2-ethyl-6-(tert-pentyl)phenol),4,4′-(perfluoropropane-2,2-diyl)bis(2,6-di-tert-pentylphenol),4,4′-(perfluoropropane-2,2-diyl)bis(2-isopropyl-6-(tert-pentyl)phenol),4,4′-(perfluoropropane-2,2-diyl)bis(2-ethylphenol), and4,4′-(perfluoropropane-2,2-diyl)bis(2,6-bis(trimethylsilyl)phenol).

In order to illustrate the problems associated with existing bisphenolsorbents, FIG. 1A provides the infrared spectrum and structure of knownsorbent HCSFA2. As evidenced by the infrared spectrum, this sorbentsuffers from a high degree of self-association, which unfavorably bindsand ties up the hydroxyl (—OH) and reduces the efficacy of analytebinding. FIG. 1B further illustrates the intermolecular bonding ofHCSFA2 sorbents between hexafluoroisopropanol functional groups. FIG. 1Cdepicts the infrared spectrum and hyperbranched structure of HCSFA2. Asevidenced by the infrared spectrum, this sorbent has been found tosuffer from a high degree of self-association, which unfavorably bindsthe hydroxyl (—OH) and reduces the efficacy of analyte binding.Typically, in sorbents with hydroxyl functionality, less than 10% of thehydroxyl is in the free state at any moment in time.

In contrast, FIG. 1D shows a sterically-hindered phenolic structure inaccordance with the invention that mitigates or prevents theintermolecular bonding challenge for sorbents with hexafluoroisopropanolfunctional groups. The alkyl groups form a vapor binding pocket, buthinder the approach of neighboring and relatively large sorbentmolecules. The steric groups also reduce crystal formation, which causesthe sorbents to take the form of a viscous oil, which is desirable forsorbing analyte in analytical and trapping or protection applications. A3D model showing the steric group of the invention is also included inFIG. 1D.

FIG. 1E outlines a strategy to eliminate or reduce sorbent self-bound—OH interactions in accordance with the invention. The challenge is thatexisting sorbents have —OH tied up with adjacent —OH and —CF₃ groups(upper structure), which reduces vapor bonding opportunities for theneighboring DMMP molecule. By separating the —OH and —CF₃ groups using aconjugated phenolic system (lower structure), the invention is able tolimit sorbent-sorbent intermolecular self-bonding, and the —OH moleculesare therefore more readily available to bind with chemicals of interest.

FIG. 1G illustrates HCSFA2 sorbent-DMMP IR solutochromic spectra datasets, showing differential absorption for DMMP concentrations rangingfrom 3.9 ppm to 0.0 ppm, as well as HCSFA2 polymer absorption. Thecontributions to spectral changes with vapor exposure for: 1)Vapor-sorbent interaction sites; 2) Separation of sorbent-sorbentmolecule interactions; and 3) Vapor present in the sorbent are shown.

The bisphenol sorbents of the invention are designed to stericallyshield the phenolic hydroxyl (hydrogen-bond acidic site) from undesiredinteractions with other sorbent molecules, leaving an exclusive pocketavailable for the analytes of interest. The availability of moresorbent-analyte binding sites allows binding to more analyte moleculesper unit time in the sorbent, from the contacted phase laden withanalyte, leading to superior hypersorbents than the current standards.The analyte laden phase maybe a gaseous atmosphere or a condensed phase.In addition, the bulkier alkyl groups ortho-substituted to the phenolichydroxyl lead to more liquid-like properties than crystallineproperties, which is a desirable characteristic for these types ofsorbents.

In general, the sorbents provide a means to concentrate or traphazardous chemicals or explosives (analytes) to the sorbent phase. Theconcentration of analyte into the sorbent phase can be augmented byseveral orders of magnitude higher than that in the ambient air or thecondensed phase laden with analyte, enabling effective analyte samplingfor trapping or trace detection of chemicals. These sorbents aredesigned to have extreme hydrogen-bond acidic properties, activated byfluorine chemistries, to target the complementary hydrogen-bond basicproperties of the analytes of interest. These molecular interactions arebased on reversible physisorption-type processes, allowing thesesorbents to be reused multiple times. At thicker coating levels, thesorbent can act to trap chemicals for extended time periods at ambienttemperatures, and provides a means to effectively remove chemicals fromair or condensed phases to clean air or water for protection orfiltration type applications.

In some aspects of the invention, if the bisphenol sorbent is acrystalline solid, the sorbent may be dispersed or dissolved into aliquid or resin-like host material, which mitigates the challenge ofslow chemical diffusion into the crystalline bisphenol sorbent. Suitablehost materials may include, but are not limited to4,4′-(perfluoropropane-2,2-diyl)bis(2-(tert-pentyl)-6-propylallyl-6-(tert-pentyl)phenol),poly(dimethylsiloxane), (PDMS), poly(methylphenylsiloxane), andpoly(dimethylsiloxane-co-methylphenylsiloxane).

FIGS. 6A-6D show synthetic schemes for producing the various bisphenolsof the invention, as well as an overview of the structures ofpresently-preferred bisphenols in accordance with the invention. Schemes1-5 describe synthetic routes to sorbents that have been synthesized andcharacterized. Schemes 6-9 describe planned synthetic routes foradditional sorbent candidates. Scheme 10 shows a summary of thestructures of presently-preferred bisphenol sorbents that may besynthesized in accordance with the invention.

FIGS. 1F and 6D illustrate several presently-preferred bisphenol sorbentmolecules in accordance with the invention.

Of the newly-developed sorbents tested,4,4′-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2,6-di-tert-butylphenol]3 shows the greatest amount of free hydroxyl, as evidenced by infraredspectroscopy. There is almost solely free hydroxyl present. FIG. 2 showsthe infrared spectrum and structure of4,4′-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2,6-di-tert-butylphenol]3. As evidenced by the infrared spectrum, this sorbent shows littleevidence of self-association, which is an ideal property for thesorbents of the invention. However, this bisphenol is a powdery solid,which is not the ideal physical state for sorption of analyte moleculesin analytical, trapping or protection applications.

The newly developed sorbent4,4′-(perfluoropropane-2,2-diyl)bis(2-(tert-pentyl)-6-propylphenol) 10also shows mostly free hydroxyl in the infrared spectrum, with a smallamount of self-association evident. FIG. 3 shows the infrared spectrumand structure of4,4′-(perfluoropropane-2,2-diyl)bis(2-(tert-pentyl)-6-propylphenol) 10.This sorbent is a viscous oil, which is the ideal physical state. Thissorbent is a viscous oil, which is the ideal physical state.

In comparison, known compound4,4′-(perfluoropropane-2,2-diyl)bis(2,6-dimethylphenol) 30 was alsosynthesized to show the effect of the alkyl substituent on the degree ofself-association (see, e.g., FIG. 4; Dai, Y., et al., Macromolecules2004, 37, 1403-1410). The infrared spectrum and structure of knownsorbent compound 4,4′-(perfluoropropane-2,2-diyl)bis(2,6-dimethylphenol)30 are shown in FIG. 4. As evidenced by the infrared spectrum, thissorbent suffers from a high degree of self-association, with no freehydroxyl visible.

An overlay of the hydroxyl peaks of the infrared spectra of bisphenols3, 10, and 30 is shown in FIG. 5. Bisphenol 30, with methyl groupsortho-substituted to the hydroxyls, shows the greatest degree ofself-association. Bisphenols 3 and 10, substituted with bulkier alkylsubstituents ortho- to the hydroxyls, have substantially more freehydroxyl evident and less self-association. In FIG. 5 the absorbancevalues (y-axis) are normalized for comparison. Wavenumbers (x-axis,representing the IR shifts) have not been modified.

The sorbents of the invention are typically applied to a substrate as athin film. For gas sensing applications, this typically includescoatings measured in 10's of nanometers of thickness. For collection orprotection applications, this typically includes coatings measured in100's of nanometers to micrometers of thickness. The coatings can beapplied to any solid substrate, e.g., flat substrates, porous substratesor dense particles. The sorbents of the invention may also befunctionalized to provide reactive sites (e.g. alkenic structures), forgrafting to solid substrates, attaching to a polymer backbone as pendentgroups, or splicing into and as part of a polymer backbone. The latterhas been performed with other bisphenol structures (e.g., BSP3), asdescribed in U.S. Pat. No. 6,015,869 to Grate, J. W. et al.

The bisphenol sorbents of the invention may be provided as a layer orcoating, such as by immobilizing on a surface of a support structure, orwithin pores contained within a porous support structure. Supportstructures suitable for use as supports for the bisphenol sorbents ofthe invention include, but are not limited to, silicon, carbon, andpolymers. Examples include metal-organic frameworks (MOFs), zeolites,CARBOTRAP® adsorbent, CARBOPACK™ adsorbent, activated coconut charcoal,HAYESEP® porous polymer adsorbent, CARBOXEN® adsorbent, CARBOSIEVE®adsorbent, GRAPHSPHERE™ adsorbent, FLORISIL® adsorbent, AMBERLITE®adsorbents, and diatomaceous earth. The bisphenol sorbents of theinvention may also be coated as a chromatographic stationary phase. Theinvention is not to be considered limited to use with any particularsupport structures, which may differ depending on the particularapplication for which the bisphenol sorbents are used. The inventionfurther relates to support structures having the bisphenol sorbents ofthe invention sorbed thereto, as well as to chromatography stationaryphases having the bisphenol sorbents as the stationary phase.

By adjusting the thickness of the sorbent layer or coating on or withina support structure, enhanced retention of the analyte may be conferredsuch that collection of analyte over a period of exposure time can beachieved. Subsequent heating of the trapped analyte allows its releasefor regeneration of the sorbent or subsequent analytical operations.

By immobilization of the sorbent to a solid substrate or by fixing it tothe substrate, or by incorporating it into a porous framework, thisopens up applications to sample analyte from condensed phases such aswater. One example of a commercial device that may be used in accordancewith this aspect of the invention is a Solid Phase MicroExtraction(SPME) device. The sorbents described in this invention will findutility as coatings for SPME or related devices for air or condensedphase applications.

These sorbents can also be used for advanced sensing, trapping,protection, and analytical applications. Examples of such applicationsinclude collection, preconcentrator, gas chromatography stationaryphases, sensing, microsensor coating applications, and coatings forporous support structure or nanoparticulate materials, gas maskcartridges or other types of air filter cartridges.

For example, FIGS. 7, and 9-10 provide sample infrared (IR) spectra andQuartz Crystal Microbalance (QCM) gravimetry data, respectively. FIGS.7, 9, and 10 show IR spectra for vapor-sorbent binding and signalresponse data for a sorbent 10-coated QCM exposed to an example vapor,dimethyl methylphosphonate (DMMP) vapor. DMMP is used as a nerve agentgas simulant, as are trimethyl phosphate (TMP), and diisopropylmethylphosphonate (DIMP). The IR spectrum of bisphenol 10 beforeexposure to DMMP vapors, when interacting with DMMP vapors, and afterthe DMMP has been purged from the system are shown. While interactingwith the DMMP, the IR spectrum shows that there is a clear decrease inthe hydroxyl absorption frequency (˜3650 cm⁻¹) and a new, broadhydrogen-bonded hydroxyl frequency (˜3300 cm⁻¹). After the DMMP ispurged, the IR spectrum has returned to its initial, pre-exposure state,with the sharp hydroxyl peak reforming. The QCM sensor, containing acrystal coated with bisphenol 10, demonstrates mass uptake upon exposureto DMMP vapor, as evidenced by a pronounced frequency change. Afterremoving the DMMP source and flowing clean air over the QCM sensor, thesignal returns to the original baseline, corresponding to the reversibleremoval of DMMP from the sorbent. In some aspects of the invention, thesorbent molecules exhibit at least a 50% reduction in infrared spectralsignal for the associated hydroxyl groups as compared to sorbentmolecules not substituted with the bisphenol steric group or groups.

FIG. 8 shows the differential IR spectrum of bisphenol sorbent 10interacting with DMMP vapors. The initial, sharp hydroxyl peak of 10disappears (indicated by the negative peak at ˜3650 cm⁻¹) upon exposureto DMMP. A new, broad peak appears at ˜3300 cm⁻¹.

FIG. 9 shows the response of a QCM sensor coated with bisphenol 10 toDMMP vapors at a concentration of 1 ppm. The frequency change observed(y-axis) indicates mass (DMMP vapor) uptake. The experiment was run intriplicate to demonstrate reproducibility.

FIG. 10 is a normalized graph of the response of a QCM sensor coatedwith bisphenol 10 to DMMP vapors at a concentration of 1 ppm. The y-axisis shown in Hz, with the maximum frequency set to 0 to show absolutefrequency change. The frequency change observed (y-axis) indicates mass(DMMP vapor) uptake. The experiment was run in triplicate to demonstratereproducibility. As an alternative to the QCM sensor, a microcantileverdevice or other gravimetry sensing apparatus may be used.

The bisphenol sorbents of the invention may be used in accordance withmethods for detecting analytes that include one or more hydrogen-bondbasic groups. These methods include providing one or more of thebisphenol sorbents of the invention, which may optionally beincorporated onto or into a support material or structure. The bisphenolsorbents are then contacted with a sample that may contain one or moreanalytes of interest. When the analyte of interest is present, thebisphenol sorbent selectively binds with the analyte(s) of interest toform a bisphenol sorbent-analyte physisorption type bond. Due to thepresence of the steric groups, the bisphenol sorbent is only able tobind with analytes that have a small enough size to circumvent thesteric groups. Further selectivity is achieved due to the fact that thestrong hydrogen-bond acid groups preferentially bind to stronghydrogen-bond basic groups. This prevents false detection due to bindingwith more weakly basic interferents such as aromatic based fuels.

The detection methods of the invention may be combined with existing IRspectroscopy and mass-sensitive detection techniques in order todetermine the composition of the bound analyte.

In addition to detection methods, the invention provides methods inwhich one or more of the bisphenol sorbents of the invention are usedfor collecting analytes that have one or more hydrogen-bond basicgroups. Analytes that may be collected include toxic or hazardouschemicals, such as CWAs, TICS, and explosives. A layer of bisphenolsorbent may be provided, for example, by immobilizing the bisphenolsorbent on a support structure, or within the pores of a porous supportstructure. The bisphenol sorbent is then contacted with a sample thatcontains the analyte to be collected. The bisphenol sorbent selectivelybinds with the stronger hydrogen-bond basic analyte as compared to anyweaker hydrogen-bond basic chemicals or interferents that may bepresent. The bisphenol sorbent-analyte interaction may be defeated byheating, releasing the analyte, and permitting the bisphenol sorbentlayer to be re-used for further collections. The collection methods maybe used, for example, with Solid Phase MicroExtraction (SPME) fibers.

The bisphenol sorbents may also be used in methods for conductingchromatographic separation of mixtures of compounds including analyteshaving one or more hydrogen-bond basic groups. The bisphenol sorbents ofthe invention are provided on a chromatography stationary phase, andthen contacted with a sample that includes a hydrogen-bond basiccompound. The bisphenol sorbent selectively binds with hydrogen-bondbasic analytes having higher hydrogen-bond basicity, and any chemicalsor interferents having lower hydrogen-bond basicity that are present inthe sample are separately eluted through the chromatographic column.

The bisphenol sorbents of the invention may also be beneficially used inmethods to prevent or reduce endocrine disruption that may be causedwhen unreacted bisphenols are ingested by humans and animals, when usedin the place of conventional bisphenols not incorporating the stericprotection groups of the invention. The invention also provides methodsfor protecting the hydroxyl groups of bisphenols with the steric groupsof the invention.

Conventional bisphenols, such as bisphenol S (CAS 80-09-1), bisphenol C2(CAS 14868-03-2), bisphenol A (CAS 80-05-7), bisphenol AP (CAS1571-75-1), bisphenol B (CAS 77-40-7), bisphenol BP (CAS 1844-01-5),bisphenol C (CAS 79-97-0), bisphenol E (CAS 2081-08-5), bisphenol F (CAS620-92-8), bisphenol G (CAS 127-54-8), bisphenol M (CAS 13595-25-0),bisphenol P (CAS 2167-51-3), bisphenol TMC (CAS 129188-99-4), andbisphenol Z (CAS 843-55-0) are often used to make articles formed frompolycarbonate plastics, epoxy resins, and polyvinyl chloride. BisphenolA and Bisphenol S monomers in particular, for example, have been shownto cause endocrine disruption in humans and animals that ingest foodsand liquids packaged in, or otherwise exposed to, plastics made usingbisphenol monomers. Without wishing to be bound by theory, it isbelieved that the endocrine disruption is caused when residual bisphenolmonomers in the plastics mimick the hormone estrogen and bind to itsreceptors in the body. These reports of endocrine disruption haveresulted in efforts to reduce their use in plastics that are used tocontain foods and liquids for human and/or animal consumption.

The formed polymeric articles may include a quantity of unreactedbisphenol monomer, which can migrate out of the formed polymer over itsuseful life. In addition, as the formed polymer degrades, additionalbisphenol monomer may be released from the polymeric article. Forexample, bisphenols may diffuse out of a polymeric article at a higherrate due to polymer degradation caused by exposure to high temperature(i.e., especially temperatures of about 100° C. or greater), pH (i.e.,alkaline conditions), and UV light.

The methods of the invention for reducing or eliminating endocrinedisruption caused by the presence of bisphenols include forming apolymeric article by polymerizing a reaction mixture comprising abisphenol monomer of Formula A or Formula B, as described above. Thereaction mixture may also include one or more chemicals used to producethe polycarbonate plastics, epoxy resins, or polyvinyl chloride. Theseinclude, but are not limited to, phosgene, epichlorohydrin, catalysts,plasticizers, and stabilizers.

After the polymeric article is formed using the bisphenol monomers ofFormula A or Formula B, any unreacted bisphenol monomers or anybisphenol monomers that may be released due to degradation of thepolymer beneficially exhibit reduced levels of endocrine disruption ascompared to a polymeric article formed by polymerizing a reactionmixture comprising conventional bisphenol monomers, or any otherbisphenol not substituted with the steric groups of the invention toprotect the acidic hydrogen bonds at the hydroxyl groups.

It is believed that any protected bisphenol monomers of the inventionthat are present in an article, such as an article formed frompolycarbonate, epoxy, or PVC, are beneficially hindered from bindingwith hormone and other receptors in the body. The bioactivity of thebisphenols of the invention may be reduced or eliminated, while stillretaining their beneficial polymerization properties, allowing them tobe more safely incorporated into plastic articles, including those usedfor containing food and drink for consumption by humans and animals.

EXAMPLES

The invention will now be particularly described by way of example.However, it will be apparent to one skilled in the art that the specificdetails are not required in order to practice the invention. Thefollowing descriptions of specific embodiments of the present inventionare presented for purposes of illustration and description. They are notintended to be exhaustive of or to limit the invention to the preciseforms disclosed. Many modifications and variations are possible in viewof the above teachings. The embodiments are shown and described in orderto best explain the principles of the invention and its practicalapplications, to thereby enable others skilled in the art to bestutilize the invention and various embodiments with various modificationsas ae suited to the particular use contemplated.

Example 1 Experimental Synthetic Procedures

Reactions were carried out in flame-dried glassware under a nitrogenatmosphere using freshly distilled solvents unless otherwise noted.Reagents were purchased from Sigma-Aldrich, Alfa Aesar, Acros, orOakwood and used without further purification. Unless otherwise stated,reactions were conducted at room temperature (approximately 23° C.).Reactions were monitored by thin-layer chromatography (TLC) using Mercksilica gel 60 F₂₅₄ (0.5 mm thickness) TLC plates followed by UVvisualization and staining with iodine, potassium permanganate,vanillin, or Hanessian's stain. Flash chromatography was performed usingSilicagel LC60A (60 Å, 40-63 μm) from Oakwood Chemical. ¹H NMR spectrawere recorded on a Bruker ASCEND™ spectrometer (400 MHz) and arereported in parts per million (ppm, 6). Splitting patterns aredesignated by: s, singlet; d, doublet; t, triplet; m, multiplet; b,broad. ¹H NMR chemical shifts are referenced to the residual solventpeak 7.26 ppm for CDCl₃ and 2.05 ppm for (CD₃)₂CO. ¹³C NMR spectra wereacquired on a Bruker ASCEND™ spectrometer (100 MHz) and are reported inparts per million (ppm, δ). ¹³C data are referenced to the residualsolvent peak 77.91 ppm for CDCl₃ and 206.26 ppm for (CD₃)₂CO. Massspectra (GC-MS) were acquired on an Agilent 5975 inert XL mass selectivedetector (0) equipped with a RESTEK RTX®-5 column (CROSSBOND® 5%diphenyl/95% dimethyl polysiloxane). GC-MS temperature program: initialtemperature 50° C.; ramp at 70° C./min to 250° C.

Example 24,4′-[2,2,2-Trifluoro-1-(trifluoromethyl)ethylidene]bis[2,6-diisopropylphenol](2)

Concentrated sulfuric acid (12.4 mL, 233 mmol, 15.6 equiv) was added towater (0.86 mL, 47.7 mmol, 3.2 equiv) at 5° C.4,4′-(Hexafluoroisopropylidene)diphenol (Bisphenol AF, 5.0 g, 14.9 mmol,1.0 equiv) was added and the solution turned pink. Isopropyl alcohol(5.7 mL, 74.4 mmol, 5.0 equiv) was added to the solution, a refluxcondenser was attached, and the solution was heated to 60° C. for 3 h.Upon cooling, the solution was diluted with chloroform (50 mL) and water(50 mL), and the aqueous layer was extracted with chloroform (3×20 mL).The combined organic layers were extracted with saturated aqueous sodiumbicarbonate (2×25 mL) and brine (1×25 mL), dried over anhydrousmagnesium sulfate (MgSO₄), and the solvent was removed under reducedpressure. The resulting residue was purified via flash columnchromatography on silica gel (3-6% ethyl acetate/hexanes) to afford thebisphenol 2 as a viscous yellow oil (1.51 g, 27%); R_(f) 0.23 (10% ethylacetate/hexanes). Bisphenol 2 appears to be an unstable compound anddecomposes over time in the presence of light/oxygen, turning a blackcolor. 41 NMR (CDCl₃, 400 MHz) δ: 7.04 (s, 4H), 3.13 (sept, J=6.8 Hz,4H), 1.21 (s, 12H), 1.19 (s, 12H); GC-MS (m/z): 504 (M).

Example 34,4′-[2,2,2-Trifluoro-1-(trifluoromethyl)ethylidene]bis[2,6-di-tert-butylphenol](3)

To a 20 mL dram vial was added 4,4′-(hexafluoroisopropylidene)diphenol(1.00 g, 2.97 mmol, 1.0 equiv), tert-butyl alcohol (1.71 mL, 17.8 mmol,6.0 equiv), and sulfuric acid (0.6 mL). The solution was allowed to stirfor 24 h. The solution was diluted with water (3 mL) and the organiclayer was extracted with ethyl acetate (3×2 mL). The combined organiclayers were washed with brine (1×3 mL), dried over anhydrous MgSO₄, andthe solvent was removed under reduced pressure. The crude residue waspurified via flash column chromatography on silica gel (3-50% ethylacetate/hexanes) to afford the bisphenol 3 as a white solid (39 mg,2.3%). ¹H NMR [(CD₃)₂CO, 400 MHz] δ: 7.22 (s, 4H), 6.43 (s, 2H), 1.39(s, 36H); GC-MS (m/z): 560 (M).

Example 44,4′-(Perfluoropropane-2,2-diyl)bis(((3-methylbut-2-en-1-yl)oxy)benzene)(4)

To a solution of 4,4′-(hexafluoroisopropylidene)diphenol (5.0 g, 14.9mmol, 1.0 equiv) in anhydrous acetone (7.1 mL) was added potassiumcarbonate (5.3 g, 38.7 mmol, 2.6 equiv), and the solution was allowed tostir for 30 min. 3,3-Dimethylallyl bromide (4.3 mL, 37.2 mmol, 2.5equiv) was added dropwise and the solution was allowed to stir for 16 h.The mixture was filtered to remove remaining solids and the solvent wasremoved under reduced pressure. The residue was dissolved in diethylether, washed with brine (10 mL), and dried over anhydrous MgSO₄. Thesolvent was removed under reduced pressure to afford the ether 4 as ayellow oil (7.02 g, 100%). ¹H NMR (CDCl₃, 400 MHz) δ: 7.29 (d, J=8.8 Hz,4H), 6.88 (d, J=9.2 Hz, 4H), 5.50 (tqq, J=6.8, 1.6, 1.6 Hz, 2H), 4.52(d, J=6.8 Hz, 4H), 1.81 (s, 6H), 1.75 (s, 6H). GC-MS (m/z): 472 (M).

Example 54,4′-(Perfluoropropane-2,2-diyl)bis(2-(2-methylbut-3-en-2-yl)phenol) (6)

To a ChemGlass pressure vessel was added a stir bar,4,4′-(perfluoropropane-2,2-diyl)bis(((3-methylbut-2-en-1-yl)oxy)benzene)4 (431 mg, 0.912 mmol, 1.0 equiv), hexamethyldisilazane (0.83 mL, 3.96mmol, 4.3 equiv), and N,N-diethylaniline (1.8 mL). The vessel was sealedand heated to 200° C. for 42 h. The reaction was allowed to cool to roomtemperature and diluted with ethyl acetate (10 mL). The solution wasextracted with HCl (3.0 M, 3×3 mL), washed with saturated aqueous sodiumbicarbonate (2×3 mL) and brine (3 mL), and dried over anhydrous sodiumsulfate (Na₂SO₄). The solvent was removed under reduced pressure toafford the silyl ether 5, a brown oil, which was carried forward to thedesilylation without purification. GC-MS (m/z): 616 (M).

To a solution of the crude silyl ether 5 (0.912 mmol, 1.0 equiv) intetrahydrofuran (THF, 4.6 mL) was added tetrabutylammonium fluoride (1.0M solution in THF, 3.2 mL, 3.2 mmol, 3.5 equiv) dropwise. The solutionwas allowed to stir for 16 h and then quenched with brine (5 mL). Theaqueous layer was extracted with diethyl ether (3×3 mL). The combinedorganic layers were washed with saturated aqueous ammonium chloride (5mL) and brine (5 mL), dried over anhydrous MgSO₄, and the solvent wasremoved under reduced pressure. The resulting residue was purified viaflash column chromatography on silica gel (5-17% ethyl acetate/hexanes)to afford the alkene 6 as a viscous pale yellow oil (196 mg, 45% over 2steps); R_(f) 0.13 (10% ethyl acetate/hexanes). ¹H NMR (CDCl₃, 400 MHz)δ: 7.23 (m, 4H), 6.82 (dd, J=7.2, 2.0 Hz, 2H), 6.19 (dd, J=17.6, 10.4Hz, 2H), 5.98 (s, 2H), 5.36 (dd, J=17.6, 0.8 Hz, 2H), 5.33 (dd, J=10.4,0.8 Hz, 2H), 1.35 (s, 12H). GC-MS (m/z): 472 (M).

Example 6 4,4′-(Perfluoropropane-2,2-diyl)bis(2-(tert-pentyl)phenol) (7)

In a glove box, palladium on carbon (10%, 34 mg, 31.9 μmol, 8 mol % Pd)was added to a round-bottom flask. The flask was removed from the glovebox and placed under a nitrogen atmosphere. Ethanol (4.2 mL) and4,4′-(perfluoropropane-2,2-diyl)bis(2-(2-methylbut-3-en-2-yl)phenol) 6(196 mg, 0.415 mmol, 1.0 equiv) were added to the flask. The nitrogenatmosphere was then replaced with a hydrogen balloon and the solutionwas allowed to stir for 36 h. The reaction mixture was then filteredover a pad of Celite, flushed with ethanol, and the solvent was removedby rotary evaporation. The crude reaction mixture was purified via flashcolumn chromatography on silica gel (17% ethyl acetate/hexanes) toafford the bisphenol 7 as a viscous, pale yellow oil (191 mg, 97%yield); R_(f) 0.33 (20% ethyl acetate/hexanes). ¹H NMR (CDCl₃, 400 MHz)δ: 7.16 (d, J=8.8 Hz, 2H), 7.11 (s, 2H), 6.63 (d, J=8.8 Hz, 2H), 4.88(s, 2H), 1.79 (q, J=7.6 Hz, 4H), 1.25 (s, 12H), 0.60 (t, J=7.6 Hz, 6H).GC-MS (m/z): 476 (M).

Example 74,4′-(Perfluoropropane-2,2-diyl)bis(1-(allyloxy)-2-(tert-pentyl)benzene)(8)

To a dram vial containing4,4′-(perfluoropropane-2,2-diyl)bis(2-(tert-pentyl)phenol) 7 (70 mg,0.147 mmol, 1.0 equiv) was added anhydrous acetone (0.3 mL) andpotassium carbonate (134 mg, 0.970 mmol, 6.6 equiv). The solution wasallowed to stir for 30 min, and then allyl bromide (80 μL, 0.924 mmol,6.3 equiv) was added. After the solution was allowed to stir for 2 h,thin-layer chromatography (20% ethyl acetate/hexanes) indicated thereaction was incomplete. Acetone (1.0 mL), potassium carbonate (65 mg,0.470 mmol, 3.2 equiv), and allyl bromide (40 μL, 0.462 mmol, 3.1 equiv)were added and the solution was allowed to stir for an additional 12 h.The mixture was filtered to remove remaining solids and the solvent wasremoved under reduced pressure. The residue was dissolved in diethylether, washed with brine (5 mL), and dried over anhydrous MgSO₄. Thesolvent was removed by rotary evaporation to afford the ether 8 as aviscous, pale yellow oil (64 mg, 78% yield). ¹H NMR (CDCl₃, 400 MHz) δ:7.27 (s, 2H), 7.11 (s, 2H), 6.81 (d, J=8.8 Hz, 2H), 6.09 (ddt, J=17.2,10.4, 5.2 Hz, 2H), 5.44 (ddt, J=17.2, 3.2, 1.6 Hz, 2H), 5.29 (ddt,J=10.4, 2.8, 1.6 Hz, 2H), 4.58 (ddd, J=5.2, 1.6, 1.6 Hz, 4H), 1.81 (q,J=7.2 Hz, 4H), 1.23 (s, 12H), 0.56 (t, J=7.2 Hz, 6H).

Example 84,4′-(Perfluoropropane-2,2-diyl)bis(2-allyl-6-(tert-pentyl)phenol) (10)

To a scintillation vial containing4,4′-(perfluoropropane-2,2-diyl)bis(1-(allyloxy)-2-(tert-pentyl)benzene)8 (61 mg, 0.110 mmol, 1.0 equiv) was added N,N-diethylaniline (0.22 mL).The solution was heated to 200° C. and allowed to stir for 40 h. Thesolution was allowed to cool to room temperature and diluted with ethylacetate (5 mL). The mixture was extracted with HCl (3.0 M, 3×3 mL),washed with saturated aqueous sodium bicarbonate (2×2 mL) and brine (3mL), and dried over anhydrous Na₂SO₄. The solvent was removed by rotaryevaporation to afford the alkene 9 as a brown oil, which was carriedforward to the hydrogenation without further purification. ¹H NMR(CDCl₃, 400 MHz) δ: 7.05 (s, 2H), 7.04 (s, 2H), 6.01 (ddt, J=16.4, 10.4,6.0 Hz, 2H), 5.29 (s, 2H), 5.23 (ddt, J=10.4, 3.2, 1.6 Hz, 2H), 5.18(ddt, J=17.2, 3.2, 1.6 Hz, 2H), 3.39 (ddd, J=6.0, 1.6, 1.6 Hz, 4H), 1.79(q, J=7.6 Hz, 4H), 1.25 (s, 12H), 0.58 (t, J=7.6 Hz, 6H).

In a glove box, palladium on carbon (10%, 25 mg, 23.5 μmol, 21 mol % Pd)was added to a round-bottom flask, which was then removed from theglovebox and placed under a nitrogen atmosphere. The crude alkene 9 (61mg, 0.110 mmol, 1.0 equiv) and ethanol (2.1 mL) were added to the flask.The nitrogen atmosphere was then replaced with a hydrogen balloon andthe solution was allowed to stir for 60 h. The reaction mixture was thenfiltered over a pad of Celite, flushed with ethanol, and the solvent wasremoved by rotary evaporation. The crude residue was purified via flashcolumn chromatography on silica gel (4% ethyl acetate/hexanes) to affordthe bisphenol 10 as a viscous, pale yellow oil (29 mg, 47% over 2steps); R_(f) 0.40 (10% ethyl acetate/hexanes). ¹H NMR (CDCl₃, 400 MHz)δ: 7.04 (s, 2H), 7.00 (s, 2H), 4.95 (s, 2H), 2.52 (t, J=7.6 Hz, 4H),1.80 (q, J=7.2 Hz, 4H), 1.61 (tq, J=7.6, 7.6 Hz, 4H), 1.26 (s, 12H),0.95 (t, J=7.2 Hz, 6H), 0.60 (t, J=7.6 Hz, 6H). GC-MS (m/z): 560 (M).

Example 94,4′-(Perfluoropropane-2,2-diyl)bis(1-(allyloxy)-2-propylbenzene) (12)

To a scintillation vial containing2,2-bis(4-hydroxy-3-propylphenyl)hexafluoropropane¹ 11 (349 mg, 0.830mmol, 1.0 equiv) was added anhydrous acetone (1.5 mL) and potassiumcarbonate (607 mg, 4.39 mmol, 5.3 equiv). The solution was allowed tostir for 30 min, and then allyl bromide (0.36 mL, 4.16 mmol, 5.0 equiv)was added. After the reaction was allowed to stir for 2.5 h, thin-layerchromatography (20% ethyl acetate/hexanes) indicated the reaction wasstill incomplete. Potassium carbonate (596 mg, 4.31 mmol, 5.2 equiv) andally bromide (0.36 mL, 4.16 mmol, 5.0 equiv) were added and the reactionwas allowed to stir for an additional 16 h. The mixture was filtered toremove remaining solids and the solvent was removed under reducedpressure. The residue was dissolved in diethyl ether, washed with brine(5 mL), and dried over anhydrous MgSO₄. The solvent was removed byrotary evaporation to afford the ether 12 as a viscous, pale yellow oil(331 mg, 80%). ¹H NMR (CDCl₃, 400 MHz) δ: 7.20 (d, J=8.4 Hz, 2H), 7.08(s, 2H), 6.78 (d, J=8.8 Hz, 2H), 6.06 (ddt, J=17.2, 10.4, 4.8 Hz, 2H),5.44 (ddt, J=17.2, 3.2, 1.6 Hz, 2H), 5.28 (ddt, J=10.4, 3.2, 1.6 Hz,2H), 4.56 (ddd, J=4.8, 1.6, 1.6 Hz, 4H), 2.57 (t, J=7.6 Hz, 4H), 1.56(tq, J=7.6, 7.6 Hz, 4H), 0.88 (t, J=7.6 Hz, 6H).

Example 10 4,4′-(Perfluoropropane-2,2-diyl)bis(2-allyl-6-propylphenol)(14)

To a ChemGlass pressure vessel was added4,4′-(perfluoropropane-2,2-diyl)bis(1-(allyloxy)-2-propylbenzene) 12(331 mg, 0.661 mmol, 1.0 equiv) and N,N-diethylaniline (1.3 mL). Thesolution was heated to 200° C. and allowed to stir for 40 h. Thesolution was allowed to cool to room temperature and diluted with ethylacetate (5 mL). The mixture was extracted with HCl (3.0 M, 3×3 mL),washed with saturated aqueous sodium bicarbonate (2×3 mL) and brine (3mL), and dried over anhydrous Na₂SO₄. The solvent was removed underreduced pressure to afford the alkene 13 as a brown oil, which wascarried forward to the hydrogenation without further purification.

In a glove box, palladium on carbon (10%, 49 mg, 46.3 μmol, 7 mol % Pd)was added to a round-bottom flask, which was then removed from theglovebox and placed under a nitrogen atmosphere. The crude alkene 13(331 mg, 0.661 mmol, 1.0 equiv) and ethanol (6.6 mL) were added to theflask and the nitrogen atmosphere was subsequently replaced with ahydrogen balloon. The solution was allowed to stir for 60 h, filteredover a pad of Celite, and the Celite was flushed with ethanol. Thesolvent was removed by rotary evaporation and the crude residue waspurified via flash column chromatography on silica gel (9% ethylacetate/hexanes) to afford the bisphenol 14 as a waxy yellow solid (289mg, 87% over 2 steps). ¹H NMR (CDCl₃, 400 MHz) δ: 6.97 (s, 4H), 4.76 (s,2H), 2.53 (t, J=7.6 Hz, 8H), 1.59 (tq, J=7.6, 7.6 Hz, 8H), 0.93 (t,J=7.6 Hz, 12H).

It will, of course, be appreciated that the above description has beengiven by way of example only and that modifications in detail may bemade within the scope of the present invention.

Throughout this application, various patents and publications have beencited. The disclosures of these patents and publications in theirentireties are hereby incorporated by reference into this application,in order to more fully describe the state of the art to which thisinvention pertains.

The invention is capable of modification, alteration, and equivalents inform and function, as will occur to those ordinarily skilled in thepertinent arts having the benefit of this disclosure. While the presentinvention has been described with respect to what are presentlyconsidered the preferred embodiments, the invention is not so limited.To the contrary, the invention is intended to cover variousmodifications and equivalent arrangements included within the spirit andscope of the description provided above.

What is claimed:
 1. A method for separating a hydrogen-bond basicanalyte from a mixture, the method comprising: coating a bisphenolsorbent comprising a compound of formula I or formula II as achromatographic stationary phase,

wherein R¹ is selected from the group consisting of prop-1-en-2-yl;-dimethyl(phenyl)silyl; trimethylsilyl; diphenylmethyl; methylthio;prop-2-enyl; benzyl; ethylthio; cyclopropyl; 2-(trimethylsilyl)ethyl;2,2-dimethylpropyl; 2-methylpropyl; phenylethyl; propyl; butyl;sec-butyl; pentyl; heptyl; propan-2-yl; cyclopentyl; cyclohexyl;cyclobutyl; 3-ethylpentan-3-yl; ethyl; 1,1-dimethylpropyl;(trimethylsilyl)methyl; trifluoromethyl; and fluoro; and R² is selectedfrom the group consisting of hydrogen, methyl; tert-butyl;prop-1-en-2-yl; dimethyl(phenyl)silyl; trimethylsilyl; diphenylmethyl;methylthio; prop-2-enyl; benzyl; ethylthio; cyclopropyl;2-(trimethylsilyl)ethyl; 2,2-dimethylpropyl; 2-methylpropyl;phenylethyl; propyl; butyl; sec-butyl; pentyl; heptyl; propan-2-yl;cyclopentyl; cyclobutyl; 3-ethylpentan-3-yl; ethyl; 1,1-dimethylpropyl;(trimethylsilyl)methyl; trifluoromethyl; and fluoro; and contacting thechromatographic stationary phase coated with bisphenol sorbent with asample comprising a hydrogen-bond basic analyte, wherein the bisphenolsorbent selectively binds with hydrogen-bond basic analytes havinghigher hydrogen-bond basicity over other chemicals having lowerhydrogen-bond basicity.